Method of controlling insect pests with dihydric fluoroalcohols



United States Patent 3,396,227 METHOD OF CONTROLLING INSECT PESTS WITH DIHYDRIC FLUOROALCOHOLS Everett E. Gilbert, Morristown, N..I., assignor to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Aug. 11, 1965, Ser. No. 478,984

11 Claims. (Cl. 424-343) This invention relates to a method for controlling various biological pests, including insects, mites, nematodes and unwanted vegetation by the application to the pests or their hosts of certain dihydric fiuoroalcohols prepared by the reaction of perhaloacetones with alpha olefins at a 2:1 molar ratio.

I have found the resulting compounds and certain of their monoand dialkali metal and monoand diarnmonium salts are active preand post-emergence herbicides, as well as insecticides, miticides and nematocides.

Compounds suitable for use as pesticides according to my invention are the dihydric fluoroalcohols shown below and the monoand dialkali metal and monoand diammonium salts of those compounds wherein all the X groups are fluorine.

In the above formula R is a member selected from the group consisting of phenyl and lower alkyl groups of 1 to 3 carbon atoms, and X is a member selected from the group consisting of fluorine and chlorine.

The fluoroalcohols used in my invention can be prepared by reacting two moles of perhaloacetone with one mole of an alpha alkene such as isobutylene and alpha methyl styrene, as described in copending application, Ser. No. 157,270, of Morton H. Litt and George J. Schmitt, filed Dec. 5, 1961, now US. Patent No. 3,342,- 187 and shown in the equation below.

When R in the alkene shown above is a lower alkyl radical, I have found that minor proportions of the structural isomers shown below are formed in amounts ranging from about 25% to 35% of the total yield in which the double bond has moved from the primary chain to the R side chain.

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When reference is made herein to the l,3-bis(l,3-hexahalo-Z-hydroxy-Z-propyl)-2-alkyl-1-propenes, the term is intended to include mixtures of the stated compound with minor proportions of its double bond-variant isomer as described.

The resulting dihydric fiuoroalcohols are solids only slightly soluble in water.

The monalkali metal and ammonium salts of the above fluoroalcohols, of which the alkali metal salts are watersoluble solids, the ammonium salt is water insoluble, can be prepared from those of the above alcohols in which all the X members are fluorine, by simply mixing the alcohols with an aqueous alkali metal hydroxide or anhydrous ammonia.

The dialkali metal and diammoniu-m salts can also be prepared, but require the use of large excesses of alkali and long reaction times.

Among the compounds useful as pesticides according to my invention are the following I. 1,3-BIs- (1,3-DICHLOROTETRAFLUORO-2-HYDROXY- 2-PROPYL) 2-PHENYLJ-PROPENE GF Ol C-C-OH CFaCl CFzCl 1110-0 011 (IF- C1 II. 1,3 BIS (HEXAFLUORO-2-HYDROXY-2-PROPYL) 2-PHENYL-1-PROPEN E III. 1,3-BIS HEXAFLUORO-2-HYDROXY2-PROPYL) -2- 2-PHENYL-1-PROPENE-MONOSODIUM SALT IV. 1,3-BIS(HEXAFLUORO-2-HYDROXY 2 PROPYL)-2- METHYL-LPROPENE AND MINOR AMOUNTS OF 1,3- BIS(HEXAFLUORO-2'HYDROXY-2-PROPYL) -2 METH- YLENE PROPANE V. 1,3-BIS (HEXAFLUORO 2-HYDROXY-2-PROPYL) -2- METHYL-LPROPENE MONOSODIUM SALT VI. 1.3-BIS (1,3DICHLOROTETRAFLUORO 2 HYDROXY- 2-PROPYL) 2 METHYL 1 PROPENE WITH MINOR AMOUNTS OF 1,3-(1,3-DICHLOlROTETRAFLUO'RO-2-H'Y- DROXYQ-PROPYL) 2-METHYLENE PROPANE VII. DISODIUM SALT OF 1,3-BIS(HEXAFLUORO-2-HY- DROXY2-PROPYL) -2-METHYL1-PROPENE The compounds described herein have strong biocidal activity in a number of important fields to combat or control such pests by contacting such pests either directly or by application of the compounds to the environment or habitat or host of the pest. They can be employed as herbicides in combatting unwanted vegetation in either preemergence or post-emergence application to soils and/or plants.

In the insecticidal field, control of many noxious pests can be effected by contacting the pests or their environment, their food or the host, such as insect infested plants, soils, etc., with the dihydric fiuoroalcohol compounds and salts of the perfluoro compounds. Among the insects which can be controlled by the process of my invention are Mexican bean beetles (Epilachna varz'vestis) Southern armyworms (Prodenia eridania), pea aphids (Macro- .siphum pisi), two-spotted spider mites (Ten-qnychus telarius), house files (M usca domestica) and many others, which are affected thereby in either adult, nymph, larval or egg form. Nematode control can also be effected by the process of my invention.

When reference is made herein to contacting biological pests with the compound of the invention, it is to be understood to include not only direct contacting, but also such contact achieved through treatment of the environment, habitat, food or host of such pests.

Application of the toxicant can be made in conventional manner, in admixture with a carrier. Usually the toxic compounds are mixed with at least one diluent, either solid or liquid, and are applied to the pest or its host, for example, as a finely divided dust, coarse granules or pellets, solvent solutions or aqueous sprays. The alcohols of my invention and the ammonium salts which are relatively insoluble in water can be prepared in the form of aqueous dispersions by dissolving the alcohol in a solvent such as xylene and dispersing the solution in water with the aid of anionic, cationic, or non-ionic wetting, dispersing, or emulsifying agents. In the case of the highly water-soluble alkali metal salts of the alcohols from hexafluoroacetone, these compounds can be dissolved in water alone and applied as water solutions, as well as being applied in dispersions if desired. Concentrations of toxicant will depend on the sensitivity of the pest organisms to be controlled. Usually concentrations between about .03% and about 3.0% are sufiicient.

Dusts, granules, pellets and Wettable powders can also be used in applying the dihydric fiuoroalcohol compounds or their salts according to my invention. For the preparation of dusts the alcohol or the appropriate salt thereof may be mixed in finely divided solid form with suitable powders including finely divided dry solid talc, clays such as attapulgite, kaolin, or fullers earth, wood flour, or other inert solid carriers of the type commonly employed in formulating pesticidal powder compositions.

These powders may be granulated or pelleted; or solutions or the dihydric fiuoroalcohol carbonates may be impregnated into granular or pelleted carriers of mineral and vegetable origin. Wettable powder formulations, suitable for dispersing in water and applying the water dispersion to the soil, plants or insects, etc., are prepared by incorporating in any of the finely divided powders, small amounts of surface active materials, for example, about 1% to about 5% by weight, which serve to maintain the finely powdered composition dispersed in water with which it is mixed.

Suitable surface active materials adapted for use in making both liquid and solid dispersions are anionic, cationic, or non-ionic wetting dispersing and emulsifying agents commonly employed in the formulation of Wettable powder compositions, for example, as listed by J. W. McCutcheon in Soap and Chemical Specialties, December 1957 and January, February, March and April 1958. These include the alkali metal and ammonia salts of long chain aliphatic carboxylic acids, sulfonates of the aromatic or long chain aliphatic hydrocarbons, such as sodium alkyl sulfates and sulfonates, alkyl aryl sulfonate salts, sulfonates of glycerides and their fatty acids and sulfomates of derivatives of fatty acid esters.

Example l.-Preparation of monosodium salt of 1,3-bis- (hexafluoro-2-hydroxy-2-propyl)-2-methyl-1-propene (A) Eighty grams (0.206 mole) of 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-methyl-1-propene prepared by reaction of isobutylene and hexafluoroacetone at 1:2 molar ratio was mixed with 42 ml. (0.21 mole) of 5 N aqueous sodium hydroxide and the mixture was heated at the boiling point for 15 minutes producing a clear solution. The reaction mixture was vacuum dried for 5 days resulting in a white, free-flowing powder melting at 5558 C. The yield was grams which corresponds to a theoretical yield for the monohydrated, monosodium salt.

Analytical data are shown below in comparison to calculated data for the monoand disodium salts with Calculated:

Mono Na Salt:

(B) Example 1A was repeated except that an excess of sodium hydroxide was used, i.e., 20 ml. 1 N aqueous NaOH equivalent to 0.020 mole, with 2.0 grams, 0.00515 mole of the isobutylene hexafluoroacetone reaction product. The reactants were refluxed for 1 hour and were then allowed to cool to room temperature, i.e., about 25 C., extracted with 50 ml. ethyl ether, and evaporated to dryness. The solid was recrystallized once from benzene and dried for 24 hours at 60 C. in vacuo. They melted at 226230 C. Elemental analysis showed:

Found: C, 29.0; H, 2.5; Na, 5.7.

(C) A third sodium salt was prepared by refluxing the reaction product of isobutylene and hexafluoroacetone of Example 1-A with an excess of 4 N aqueous sodium hydroxide for 24 hours, cooling, and separating the resulting crystals and drying the crystals to constant weight in vacuo at C. The resulting compound melted at 230-235 C. and had the following elemental analysis:

Found: C, 29.3; H, 2.3; Na, 6.0.

Example 2.-Preparation of disodium salt The 1:2 molar adduct of isobutylene and hexafluoroacetone was heated to boiling with a tenfold molar excess of 10 N aqueous NaOH and was then cooled to crystallization. The resulting crystals were separated by filtration and recrystallized twice from toluene. A second sample was similarly prepared except that refluxing and stirring was continued overnight.

Both samples melted over the range 103-200" C. Both samples were analyzed for carbon, hydrogen, sodium and water with the results shown below indicating the prodnet to be the disodium dihydrate.

Found: C, 25.64; H, 2.34; Na, 8.3.

Example 3.Preparation of sodium salt of 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-phenyl-1-propene Twenty-seven grams (0.06 mole) of 1,3-bis(hexafiuoro- 2-hydroxy-2-propyl)-2-phenyl-1-propene produced by reaction of a-methyl styrene and hexafluoroacetone in 1:2 molar ratio, were mixed with 2.6 grams (0.065 mole) of 5 N aqueous sodium hydroxide and 10 ml. of water. The mixture was warmed for 20 minutes on a hot plate. The resulting solution was dried 5 days in vacuo and yielded 29 grams of the monosodium salt as a dry white powder corresponding to a 100% theoretical yield of monohydrated monosodium salt, which was completely watersoluble.

6 Example 4 for injury rating with results shown in Table III below. The compounds listed in Table I were tested as pre- T CPmPOIJIIdS tested were V and VII ldenemergence and post-emergence herbicides in Standard a Ia V Macroscreening greenhouse tests according to the method of Shaw and Swanson described in Weeds, Volume 1, 5

No 4 p g 365 TABLE IIL-PRE-EMERGENCE TESTS ON GRASSES Table I.-Compounds Tested as Weed Killers Compound No. Injury t g (I) 1,3-bis( l,3-dichlorotetrafluoro-2-hydroxy-2-propyl)- Crabgrass Johnson Grass 2-phenyl-1-propene. 5 8 (II) 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-phenyl-1- t; 1g

PIOPEHS. 3 5

(III) Monosodium salt of 1,3-bis(hexafluoro-Z-hydroxy- 2-propyl -2-phenyl-1-propene.

(IV) 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-methyl-1- propene.

(V) Monosodium salt of 1,3-bis(hexafluoro-Z-hydroxy-Z- propyl) -2-methy1-1-propene.

The above tests indicate good to excellent control of crabgrass and Johnson grass by the indicated compounds.

(VI) 1,3-bis(1,3-dichlorotetrafluoro-2-hydroxy-2-propyl)- Example 6 y -p p 2 The com ounds listed below were tested for insecti- Disodium Saltof13'bis(hEXafiUOIO'Z'hYdIOXY'Z 0 cidal activitg against one or more of the pests, Mexican P Py 'p bean beetles, pea aphids, Southern armyworms and two- In the p tests, the tOXiCaht, dispersed in a spotted spider mites, by preparing suspensions in acetone liquid Such as aCelene water, was p y within one of the compounds and adjusting them' to concentrations day after Seeding, Onto Seeded flats Contained test P of 2 pounds of toxicant per 100 gallons of suspension. Seed Species and test weed Seed p at 3 Volume of Compound I below was also tested at concentrations of p y equal to gallons of spray P acre and at eolleenlb. per 100 gallons. The suspensions were then sprayed trat of lexical P acre of 16, 8 0T 4 Pounds P in the standard manner onto the leaves of the bean acre. Immediately otter spraying, the test flats were subla t 2 o d o the upper surface and 5 seconds irrigated and the needed moisture maintained during the 30 on th u de rf Aft r spraying, the deposits were following y test P dllfillg which the flats were allowed to dry on the plants and the particular pests held in the greenhouse for Observation, and were then being tested Were confined in cages on the treated leaves. rated as described hereinafter. In the post-emergence tests, Th days ft t eat ent the plants wer ob erved and s with P and weed Seedlings were treated 8 to 10 mortality records taken in percent kill of the pest.

days after seeding with the indicated toxicant at a rate Th compounds h tested were; equivalent to 16, 8 or 4 pounds per acre, and held for a 10 to 12-day observation period, which after they were (I) 1,3-bis(1,3-dichlorotetrafluoro-2-hydroxy-2-prorated. pyl)-2-phenyl-1-propene.

In both the pre-emergence and post-emergence tests, (II) 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-phenylsimilarly seeded but untreated flats were held for coml-propene.

parison. The response of the test plant to the toxicant was (III) Monosodium salt of l,3-bis(hexafluoro-2-hymeasured by injury rating (IR) on a scale of 0 to 10; droxy-Z-propyl)-2-phenyl-1-propene. 0 indicating no injury, 10 indicating complete kill of the (IV) 1,3-bis(hexafluoro-2-hydroxy-2-propy1)-2-methtest plants. Percent mortality (PK), a calculated index, yl-l-propene. is obtained by comparing the mortality in the toxicant (V) Monosodium salt of 1,3 bis(hexafluoro-2-hytreated flats with that in the untreated flats. Results of d-roxy-Z propyl)-2-methy1-l-propene. both pre-emergence and post-emergence tests are shown (VI) 1,3-'bis(1,3-dichlorotetrafluoro-2-hydroxy-2-proin Table II. pyl)-2-rnethyl-1-propene.

TABLE II Pre-emergence Post-emergence (IR Com-1 Lbs. Corn Cotton Wheat Soybeans Rye grass Rape Crops Weeds Crops poun per No. acre 1R1 PK2 IR PK IR PK IR PK IR PK IR PK Corn Cotton Wheat Soy Av. Rye Rape Av. 23s

beans grass average 1 10 9 9 7 s 9 9 s i 1g 13 g 10 10 9 "'EY' U E' O 0 0 2 is 6 10 "1'66" 2 10 5 9 s s 5 1g 1529100044010100110610771097 0 0 o 0 1 0 1 0 6 60 10 100 2 1o 4 9.5 6 10 10 10 s 0 0 3 1s 5 50 1 0 7 70 10 100 3 9.5 9.5 5 7 1o 10 10 s 11013110033010100410710891098 006505375258809902545453965 1 IR=Injury Rating; 0=No Injury, l0=Co1nplete Kill. 2 PK=Percent kill.

It will be noted from Table II that the compounds of Results of the tests are shown in Table IVbelow. the invention show excellent selective pre-emergence kill TABLE v of broadleaf Weeds, as exemplified by rape, with little P k, or no crop injury. Post-emergence tests showed good to ment mof excellent nonselective contact activity, especially on gg fif g g 23 j p Southern Tv v o- 81111 orm S 0 broadleaf plants. larvae adults lai ae s isi ae r Example 5 mltes 2 25 100 100 100 100 Four compounds were subjected to pre-emerg n riIIIIIIIIII 2' 1%?) 1% tests against crabgrass and Johnson grass with the toxig g 25 0 cant applied at the rate of 16 pounds per acre, using the 'j 2 ";5""jjjjjjjjjjjj jgg 32 method described in Example 4 above and observed 75 2 00 109 100 7 Example 7 The compounds listed below were tested for nematocidal activity by formulating solutions of the toxicant 8 (VI) 1, 3-bis( 1,3-dichlorotetrafluoro-2-hydroxy-2propyl) 2-methyl-1 -propene are shown in Table VI below.

TABLE VI Percent N 0. Percent kill Eggs Larval on bait flies laid condition 7 days 8 days 9 days 10 days 0625 48 100 0313 47 89. 4 0156 44 0 50 100 43 100 125 47 100 0313 50 98 98 None- 0156 46 37 52. 2 Many--- Normal 1.0 45 100 one None. Cheek None. 43 0 0 es Normal as acetone solutions (48 grams/100 ml.) and diluting the solutions with water to 0.1% (1,000 parts per million) of toxicant. Into each of three small petri dishes were placed 5 ml. of the toxicant solution and approximately 100 nematode worms were placed in each solution. The dishes were held in a dark room at temperatures of 75 to 80 F. Observations of the worms after 1, 2 and 3 days were made to determine the percent mortality of the worms.

In the above test, compounds III, the monosodium salt propene; V, the monosodium salt of l,3-bis(hexafluoro- 2 hydroxy 2 propyl)-2-methyl-1-propene; IV, 1,3- bis(hexafluoro 2 hydroxy-2-propyl)-2-methyl-l-propene and VI, 1,3 bis(l,3-dichlorotetrafluoro-2-hydroxy- 2 propyl) 2 methyl-l-propene gave results shown in Table V below.

TABLE V Percent mortality Compound No.

1 day 2 days 3 days Example 8 The compounds listed below were tested as t-oxicants against house flies (Musca domestica) by preparing a bait mixture of powdered milk, granulated sugar and powdered egg and adding thereto solutions or suspensions of the toxicant in amounts of 0.5% or less of the bait. The bait is then allowed to dry and is repulverized. The treated food is then placed in emergence cages containing 50 fly pupae. Cages containing untreated food were used as checks. Examinations of each cage were made periodically to determine emergence, condition of flies and acute toxicity. Nine days after start of test, oviposition medium was placed in each cage, and on the following day the medium was examined for eggs, and if none were present, the medium moistened and examined daily until oviposition occured or all adults were dead. Egg viability was determined by inspecting the medium for growing larvae 2 to 3 days after oviposition.

Results of these tests on compounds:

(I) l,3-bis(1,3-dichlorotetrafluoro-2-hydroxy-2-propyl)- Z-phenyl-l-propene;

(II) 1,3-bis(hexafluoro-Z-hydroxy-2-propyl)-2-phenyl-1- propene;

(III) monosodium salt of 1,3-bis(hexafluoro-Z-hydroxy- 2-propyl)-2-phenyl-1-propene;

(IV) 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-methyl-lpropene;

(V) monosodium salt of 1,3-bis(hexafluoro-Z-hydroxy- 2-pr0pyl)-2-methyl-1-propene; and

It will be seen from Table VI that the compounds of the invention are excellent toxicants against house flies even at exceedingly low concentrations.

While the above describes the preferred embodiments of my invention, it will be understood that departures can be made therefrom within the scope of the specification and claims.

I claim:

1. The method for controlling soil-infesting nematodes, mites, house flies and other insect pests which comprises contacting such pests with a toxic amount of a compound selected from the group consisting of (1) compounds of the formula wherein R is a member selected from the group consisting of phenyl and lower alkyl groups of 1 to 3 carbon atoms, and X is a member selected from the group consisting of fluorine and chlorine and (2) monoand dialkali metal and monoand diammonium salts of-the compounds of the said formula wherein all the X substituents are fluorine.

2. The method of claim 1 wherein mites or insects are contacted with the toxic compound.

3. The method of claim 1 wherein soil-infesting nematodes are contacted with the toxic compound.

47 The method of claim 1 wherein house flies are contacted with the toxic compound admixed with house-fly food bait.

5. The method according to claim 1 wherein the toxic compound is 1,3-bis(1,3-dichlorotetrafluoro-2-hydroxy-2- propyl)--2-phenyl-l-propene.

6. The method according to claim 1 wherein the toxic compound is 1,3-bis(hexafiuoro-Z-hydroxy-Z-propyl)-2- phenyl-l-propene.

7. The method according to claim 1 wherein the toxic compound is a sodium salt of l,3-bis(hexafluoro-2-hydroxy-Z-propyl)-2-phenyl-1-propene.

8. The method according to claim 1 wherein the toxic compound is 1,3-bis(hexafluoro-2-hydroxy2-propyl)-2- methyl-l-propene.

9. The method according to claim 1 wherein the toxic compound is a sodium salt of 1,3-bis(hexafluoro-2-hydroxy-2-p ropyl -2-methyll-prop ene.

10. The method according to claim 1 wherein the toxic compound is 1,3-bis(1,3-dichlorotetrafluoro-2-hydroxy) -2-methyl-1-propene.

11. A composition of matter comprising (a) a quanity toxic to house flies and/or other insect pests of a compound selected from the group consisting of (1) compounds of the formula wherein R is a member selected from the group consisting of phenyl and lower alkyl of 1 to 3 carbon atoms and X is a member selected from the group consisting of fluorine and chlorine; and (2) monoalkali metal and ammonium salts of the compounds of the said formula wherein all the X substituents are fluorine, and (b) a house fly or insect bait food carrier therefor.

References Cited UNITED STATES PATENTS 6/1967 Szabo et a1. 16722 6/1967 Litt et a1. 260-633 LEWIS GOTTS, Primary Examiner.

S. K. ROSE, Assistant Examiner. 

1. THE METHOD FOR CONTROLLING SOIL-INFESTING NEMATODES, MITES, HOUSE FLIES AND OTHER INSECT PESTS WHICH COMPRISES CONTACTING SUCH PESTS WITH A TOXIC AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) COMPOUNDS OF THE FORMULA 